Reactive epoxy-onium catalysts for synthesis of polyoxazolidones

ABSTRACT

A PROCESS FOR PREPARING POLYOXAZOLIDONES IS PROVIDED IN WHICH A POLYEPOXIDE IS REACTED WITH A POLYISOCYANATE IN THE PRESENCE OF CHEMICALLY REACTIVE EPOXYONIUM CATLYSTS, SELECTED FROM THE CLASS OF AMMONIUM AND PHOSPHONIUM HALIDES HAVING AT LEAST ONE OXIRANE MOIETY. NOVEL POLYMERS ARE OBTAINED WHEN THESE NEW CATALYSTS CONTAINING TWO OR MORE ORIRANE GROUPS ARE CONDENSED WITH POLYISOCYANATES.

United States Patent REACTIVE EPOXY-ONIUM CATALYSTS FOR SYNTHESIS OFPOLYOXAZOLIDONES Gaetano F. DAlelio, 2011 E. Cedar St., South Bend, Ind.46617 No Drawing. Filed Mar. 22, 1971, Ser. No. 126,947 Int. Cl. C08g30/00 US. Cl. 260-47 EP 17 Claims ABSTRACT OF THE DISCLOSURE BACKGROUNDOF THE INVENTION The background of the invention is in the field ofsynthetic polymers prepared by reacting a polyepoxide with apolyisocyanate in the presence of specific chemically coreactivecatalysts. These polymers can be used as adhesives, coatings, inlaminating compositions, as molding compounds, caulking pastes, pottingand encapsulating substances and the like.

FIELD OF THE INVENTION This invention relates to a process for preparingpolyoxazolidones. In one aspect it relates to novel catalysts for use inthe polycondensation of a polyepoxide and a polyisocyanatle. In anotheraspect it relates to new polyoxazolidones, in which the catalyst becomesan integral part of the polymer by reaction with the polyepoxide andpolyisocyanate reactants.

DESCRIPTION OF THE PRIOR ART The synthesis of polyoxazolidones by thecondensation of polyepoxides with polyisocyanates is described in theprior patent literature. For example, US. Patent No. 3,020,262 disclosessuch a reaction in which quaternary ammonium halides are used ascatalysts. However, the process is not entirely satisfactory since thepolymerization rate is slow as a result of the limited solubility of thecatalyst, and of homo-polymerization of the polyisocyanates andpolyepoxides as side reactions. US. Pat. 3,334,110 describes a method inwhich the rate is increased by use of an aliphatic alcohol as aco-catalyst with a quaternary ammonium halide; this process requires thesubstantial elimination of alcohol to achieve practical properties inthe polymer. Organic phosphonium halides as catalysts are disclosed inmy copending application, Ser. No. 60,141, filed July 31, 1970, whichcatalysts, however, do not contain epoxide groups and are incapable ofcoreacting with the polyisocyanate or polyepoxide reactants in reactionmixture.

SUMMARY OF THE INVENTION This invention relates to a new method for thepreparation of oxazolidone derivatives. In general, it concerns the useof novel onium-halide catalysts for the condensation of polysiocyanateswith polyepoxide compounds. In particular, it refers to the use of novelcatalysts which coreact with the components in the polymerization systemand thereby become an integral part of the polymer structure. Thesecatalysts are selected from ammonium and phosphonium halides possessingat least one and no more than four oxirane moieties.

One class of catalysts used in the practice of this inventloncorresponds to the formula X R R n has a numerical value of one and two,Q represents the atoms P anl N, and

when n is one, Y represents R and when n is two, Y represents R",

wherein in which R represents a monovalent aliphatic hydrocarbon radicalcontaining at least one and no more than ten carbon atoms,

R is a monovalent radical selected from the class of R and aromatichydrocarbon radicals containing six and no more than twelve carbonatoms,

R" represents a divalent aliphatic or aromatic hydrocarbon radicalcontaining at least one and no more than twelve carbon atoms,

X represents a halogen, and

n has a numerical value of zero to ten.

Thus, when n is one, the formula of the catalyst may be written as amonoepoxide species,

Q R O R amme em, and when n is two, it may be written as a diepoxidespecies, I

E la.. 0 l L); CHR')..C oHR' 1.

Another class of epoxy-containing onium halide catalysts suitable in thepractice of this invention has the formula whereas a third class usefulin the practice of this invention is formulated as HIV) H31) 11 H t \CHRR on wherein R, R, X and n have the same meaning defined above,

and n" has a numerical value of one to three.

These catalysts are readily synthesized by well-known procedures whichinvolve quaternizing a tertiary base with an epoxy halide according tothe following equations,

X eg. 1)

l-2) wherein Q, R, R, R", X and n have the same meaning defined above.The following few specific syntheses illustrate the generalizedEquations 1 and 2, among which, Equation 3 represents the synthesis of acommercially available product:

(CHa)aN+ CICHrCHCHz (CH3)3NCH2CHCH2 0 Br Br 0 Br Br 0 In the aboveformulas, X can be any halogen, such as bromine, chlorine, iodine orfluorine, but, for reasons of economy, bromine and chlorine arepreferred. The monovalent hydrocarbon moiety, R, can be saturatedalkane, or an unsaturated alkene or alkyne, a saturated or unsaturatedcycloaliphatic and the like, such as CH a benzyl, e.g. C I-I CH CH C HCH a phenethyl, e.g., C H CH CH ClC H CH CH a cyclohexyl, e.g. C H acyclohexenyl, e.g. C H etc.; preferably R groups containing one to sixcarbon atoms are preferred for reasons of economy and reactivity. When Ris not R, it may be an aromatic hydrocarbon such as, e.g., e 5 s' 6 4 as 4, P' s s 4,

kenylene, arylene, substituted arylene and the like. Typical examples ofR" are -CH CH CH H CC-H SCH CH etc. While some R, R and R radicalscontain 0, S0 CO and Cl and therefore, are not entirely hydrocarbon,they are predominantly hydrocarbon and for the purposes of thisinvention, are regarded as such. Additional examples of R" are givenhereinafter by Z, the symbol used in the description of the polyepoxidesand the polyisocyanates.

A few typical specific examples of reactive epoxyonium catalysts, inaddition to those illustrated in Equations 3-6 inclusive are mixedammonium-phosphonium derivatives of the general formula, for example,

These epoxy-onium catalysts under the reactions of epoxides andtherefore they can react with the isocyanates as well as coreact withthe epoxide compounds present in the system. Furthermore, theseepoxy-onium catalysts react with isocyanate moieties to yieldoxazolidone moieties. This reactivity is readily established byprototype reactions with monoisocyanates, thus for example Stillfurther, when a diepoxide onium compound of this invention reacts with apolyisocyan-ate, for example, a diisocyanate, polymer formation occurswith the formation of an oxazolidone moiety, incorporting the oxoniumhalide into the molecular structure of the polymer, as illustrated bythe equation (CH3): H2N( s) aHa prepared by the procedure given in theJournal of Macromolecular Science-Chemistry, A3 (5), 1207 (1969). Thepolyepoxide reactants suitable for use in the preparation ofpolyoxazolidones are essentially unlimited. The particular polyepoxideselected for use will depend on such factors as the properties desiredin the polymer, cost, reactivity, commercial availability and onpractical as well as theoretical considerations. The polyepoxides can besaturated, unsaturated, aliphatic, cycloaliphatic, aromatic andheterocyclic, and can be written as wherein m is a numerical value of atleast two and Z is a polyvalent organic radical selected from aliphaticand aromatic structures such as alkylene, substituted alkylenes,alkyleneoxy, alkenylene, substituted alkenylene, arylene, substitutedarylene, aliphatic amide, aromatic amides and imides and the like, asshown for Z(NCO) hereinafter. Useful polyepoxides include glycidylethers derived from epichlorohydrin adducts of polyols and polyhydricphenols. A particularly suitable epoxide is the diglycidyl ether ofbisphenol A of the formula Additional examples of other polyepoxidesare:

resorcinol diglycidyl ether;

3 ,4-epoxy-6-methylcyclohexylmethyl-9, l0-epoxystearate,

1,Z-bis(2,3-epoxy-2-methylpropoxy)ethane,

the diglycidyl ether of 2,2-(p-hydroxyphenyl) propane,

butadiene dioxide,

dicyclopentadiene dioxide,

pentaerythritol tetrakis(3,4-epoxycyclohexanecarboxylate)vinylcyclohexene dioxide,

divinylbenzene dioxide,

1,5 -pentadiol bis 3,4-epoxycyclohexanecarboxylate) ethylene glycolbis(3,4-epoxycyclohexanecarboxylate),

2,2-diethyl-1,3-propanediol bis(3,4-epoxycyclohexanecarb oxylate)1,6-hexanediol bis (3 ,4-epoxycyclohexanecarboxylate) 2-butene-1,4-diolbis(3,4-epoxy-6-methylcyclohexanecarb oxylate) 1,1,1-trimethylolpropanetris(3,4-epoxycyclohexanecarboxylate 1,2,3-propanetrio1tris(3,4-epoxycyclohexanecarboxylate),

dipropylene glycol bis(2-ethylhexyl-4,5-epoxycyc1ohexane-1,2-dicarboxylate) diethylene glycolbis(3,4-epoxy-6-methylcyclohexanecarboxylate) triethylene glycolbis(3,4-epoxycyclohexanecarboxylate),

3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate,

3,4-epoxy-l-methylcyclohexylamethyl3,4-epoxy-lmethylcyclohexanecarboxylate,

bis(3,4-epoxycyclohexylmethyl) pimelate,

bis(3,4-epoxy-6-methylenecyclohexylmethyl) maleate,

bis(3,4-epoxy-6-methylcyclohexylmethyl) succinate,

bis(3,4-epoxycyclohexylmethyl) oxalate,

bis(3,4-epoxy-6-methylcyclohexylmethyl) sebacate,

bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate,

bis(3,4-epoxycyclohexylmethyl) terephthalate,

bis(3,4-epoxy-S-methylcyclohexylmethyl) terephthalate;

2,2'-sulfonyldiethanol bis(3,4-epoxycyclohexanecarb oxylate)N,N'-ethylene bis (4,5-epoxycyclohexane-1,2-dicarboximide),

di(3,4epoxycyclohexylmethyl) 1,3-tolylenedicarbamate,

3 ,4-epoxy- 6-methylcyclohexanecarb oxaldehyde acetal, 3 ,9-bis3,4-epoxycyclohexyl) -spirobi- (metadioxane) 06H, NHCOOCHzCHCHz 2 etc.

Another class of suitable polyepoxide reactant is the polyglycidylether-terminated organic polyhydric alcohols having molecular weightsfrom about 100 to 4,000, and particularly from about 150 to 1,000. Thepolyhydric alcohols, e.g., having two or three hydroxy groups, arepreferably: poly(oxyalkylene) glycols; alkylene oxide adducts ofaliphatic polyols; and polyhydroxy phenolic compounds. The alkylenegroups of the poly(oxyalkylene) glycols and alkylene oxides can havefrom two to four carbon atoms, and particularly from two to three carbonatoms. The poly(glycidyl ether) terminated polyhydric alcohols (polyols)can be represented by the formula wherein n is an integer such as two orthree, and R represents the polyol residue after removal of terminalhydroxy groups. The diglycidyl ether of bisphenol A is a satisfactoryexample of such polyepoxides, as shown in the formula given hereinabove.Illustrative of other polyglycidyl ethers of polyols of the aboveformula, there can be mentioned those prepared by the reaction of: abouttwo moles of epichlorohydrin with one mole of a polyethylene glycol orpolypropylene glycol having a molecular weight of 200, 400, or 800, orwith one mole of tetramethyleneglycol, tetrapropylene glycol and thelike, respectively, or about three moles of epichlorohydrin withtrimethylol propane or its adducts with ethyleneor propylene-oxide, etc.

Additional examples of polyepoxide compounds are given in US. Pats.3,334,110; 3,341,337; 3,415,901; 3,440,230 to which reference is herebymade.

By the term polyisocyanate is meant a compound having at least two- NCOgroups. The polyisocyanates used in the preparation of thepolyoxazolidones are represented by the formula Z'(NCO) wherein in hasthe same meaning as above. Z' represents Z but can also include radicalssuch as R"Q' where Q can be a divalent moiety such as O, OR-O, CO, CONH, CONH-, S-,

SR"S, and the like. Some typical examples of such compounds include:hexamethylene diisocyanate, xylylene diisocyanates, (OCNCH CH CH OCH 1-methyl 2,4 diisocyanatocyclohexane, phenylene diisocyanates, tolylenediisocyanates, chlorophenylene diisocyanates, polyhalophenylenediisocyanates, diphenylmethane 4,4 diisocyanate, naphthalene 1,5diisocyanate, triphenylmethane 4,4',4" triisocyanate, xyleneu,adiisothiocyanate, isopropylbenzene-a, 4-diisocyanate, etc.

Among the useful polyisocyanate reactants are included dimers andtrimers of isocyanates and diisocyanates and polymeric diisocyanates ofthe general formula and [Z'(NCO), in which x and y are two or more, aswell as compounds of the general formula, M(NCO) in which x is two ormore, and M is a polyfunctional atom or group, which includes suchcom-pounds as ethylphosphonic diisocyanate, C H P(O) (NCO)phenylphosphonic diisocyanate, C H P(NCO) compounds containing a ESiNCOgroup, isocyanates derived from sulfonamides, Z(SO NCO) and thepolyisocyanates which are obtained by phosgenation of the reactionproduct of aniline and formaldehyde as given by the following generalformula:

N00 N00 NCO wherein n equals zero to ten.

Further included among the polyisocyanates are the isocyanateprepolymers, many of which are commercially available for current use inthe preparation of polyurethane products. These prepolymers areprepared, as is well known, by end-capping polyol reactions withdiisocyanates, one mole of diisocyanate per each mole of hydroxyl groupin the presence of a catalyst, usually an organic stannate derivative.Additional examples of polyisocyanates are given in US. Pats. 3,334,110;3,415,901; 3,440,230 and 3,458,527 to which reference is hereby made.

In the absence of catalysts the reactions of an epoxide with anisocyanate does not occur at room temperature and only very slowly, ifat all, at C. In this invention, the amount of catalyst used depends onthe nature or the natures of both the polyepoxide and of thepolyisocyanates to be reacted, the temperature of the reaction and theabsence or presence of solvents which tend to decrease the rate ofreaction. Thus, when the onium halides of this invention are used ascatalysts for an epoxide-isocyanate reaction, the quantity of catalystused can vary over a wide range, from about 0.005% to 10% or more byweight of the epoxide and isocyanate reactants, the preferred rangebeing about 0.1% to 5% of the combined weight of the polyepoxide and theisocyanate, about 2% being usually an upper satisfactory limit in mostcases. However, when an onium halide is used alone to prepare a polymerby reaction with a polyisocyanate it also acts to catalyze the reactionand in equal molar ratios, it constitutes 50 mole percent of the polymerreactants, and if one-half mole of the onium halide is replaced byone-half mole of a polyepoxide, then the onium halide, as catalyst andreactant, will constitute 25 mole percent of the reactants. Similarly,if the onium halide is reacted directly with a polyepoxide, as catalystand reactant, it may constitute as much as 50 mole percent of thereactants. The onium halide catalyst may be added directly by the simpleexpediency of mixing it together with the composition components at roomtemperature in those cases where the components are liquid or not tooviscous at room temperature, or at slightly higher than room temperatureto cause a decrease in viscosity to facilitate mixing. The incorporationof the catalyst into the reaction mixture can, in all cases, whether themixture is liquid or solid, be facilitated by the use of sol-vent, ifdesired, by preparing the catalyst as a solution in a suitable solvent,preferably a solvent which does not react with the components in thereaction mixture, such as dioxane, ethyl ether, tetrahydrofuran,acetone, methyl ethyl ketone, glycol dimethyl ether, ethyl acetate, andthe like.

Most of the polyepoxides are fluid or viscous liquids at roomtemperature, or become very fluid when heated to higher temperatures ofthe order of 75100 C., and in liquid form are good solvents forpolyisocyanates, forming homogeneous solutions readily without the needof solvents. In such cases, if the practical advantage of solventlesscompositions are required in specific applications, or are desired foreconomic reasons, the catalysts can be added to the homogeneous mixtureof reactants, or it can be added to one of the reactants which is thenadded to the remainder of the reactant system. However, in some cases,when one or more of the reactants are high melting or are highlyaromatic with poor solvent properties for the other reactants, solventsare used to achieve homogeneity of the reactants. If it is desired touse a solvent initially as the reaction medium, even in those systems inwhich the reactants are mutually soluble, to prepare coatingcompositions and the like, there can be used alone,

or as mixtures with each other, such common low-cost solvents as theketones, for example, acetone, methylethyl ketones, isophorone,cyclohexanone, etc.; the esters, such as ethyl acetate, butyl acetate,isopropyl propionate, etc.; the glycol and diethylene glycol ethers,such as the dimethyl ether, the dibutyl ether, etc.; the cyclic ethers,such as dioxane, tetrahydrofuran, the halogenated solvents, such asmethylene dichloride, ethylene dichloride, trichloroethylene,chloroform, carbon tetrachloride, and the like. In those cases wheremore active solvents are required, as in the highly aromatic systems,aprotic polar solvents can be used alone or admixed with the poorerlow-cost solvents indicated above or with hydrocarbon solvents such asbenzene, toluene, heptane, cyclohexane, and the like.

A particularly useful class of active solvents are the normally liquidN,N-dia lkylcarboxylamides of which the lower molecular Weight speciesare preferred, for example, N,N dimethylformamide and N,Ndimethylacetamide, N,N-diethylformamide, N,N-dimethylmethoxyacetamide,N-methyl-caprolactam, as well as dimethyl sulfoxide, N-methyl-Z-pyrrolidone, tetramethylurea, dimethyl sulfone,hexamethylphosphoramide, formamide, N-methylformamide, butyrolactone,succinonitrile, dimethyl sulfoxide, tetramethylenesulfoxide,N-acetyl-Z-pyrrolidone, nitroethane, nitropropane, etc.

Solvents of the type indicated above can also be added during the courseof the polymerization reaction. As the reaction proceeds, a substantialincrease in viscosity of the system occurs, and solvents can be added tothe partially polymerized composition, if desired, to decrease itsviscosity for a specific application.

The polymerization reactions can be performed over a wide range oftemperatures which depend on the nature of the reactants, theconcentration of catalyst and the absence or presence of solvents fromabout room temperature to as high as up to about 200 C. At constantcatalyst concentration, the rate increases with temperature; at constanttemperature the rate increases with catalyst concentration. At highcatalyst concentrations, the reactions occur readily at ambienttemperature; at low catalyst concentrations, temperatures in the rangeof 50-150 C. are generally satisfactory and in all cases postheating, athigher temperatures up to about 200 C. can be used to assurecompleteness of the reaction.

The reaction between an epoxide moiety and an isocyanate moiety producesan oxazolidone ring,

and in the case where polyfunctional reactants are used, propagationyields the class of polymers known as polyoxazolidone, as illustrated bythe reaction between a diepoxide, symbolized for this purpose byGags/CH2):

and a diisocyanate symbolized by G'(NCO) At equal 6 molar ratios theresulting polymer is terminated by one NCO and one epoxide functionthus:

Similar considerations apply to other polyfunctional reagents when theycontain more than two functional groups, and in such cases the moleratio is based on the number of reactive groups in each reactant.

The polymerizations can be interrupted at any intermediate fluid orviscous stage for whatever use is intended, such as for filamentwinding, coating, impregnation, potting, laminating, adhesiveapplications, etc. Since the terminal groups of the polymers can undergothe reactions characteristic of such groups, they can be mixed, at anintermediate stage, with unpolymerized monoor poly-epoxides, monoorpolyisocyanates, polyols, polyamines, phenol-formaldehyde, resins,melamine-formaldehyde resins, etc., with which they can coreact further,or they can be compounded with dyes, pigments, lubricants, fillers, suchas Wood flour, alpha cellulose, cotton fibers, mica, silica, asbestos,alumina, aluminum, etc., for use as molding compounds and the like.

The polymers have a Wide range of application and uses, such as forelectrical potting, encapsulant and casting, caulking, adhesive,concrete cementing agents, filament windings, paneling and flooring,molding resins and compounds, prepegs, tooling compositions, adhesives,glass, cloth and paper laminates, electronic insulation, etc.

Numerous phosphines are available commercially for conversion to themonoand poly-epoxy onium compounds used in the practice of thisinvention by the reactions given by Equations 1-6 hereinabove. A few,among those available from commercial sources listed in the 1970-1971Laboratory Guide of the American Chemical Society, Aldrich ChemicalCompany, Inc. Catalogue Number 15, and Eastman Organic Chemicals ListNo. 45 are:

tris(dimethylamino)pliosphine, P(N(CH diphenyl-p-tolyl phosphine, p-CH CH P (C H bis-( 1,2-diphenyl phosphino)-ethane,

6 5) 2 2 2 e s 2; triallyl phosphine, (CH CHCH P trivinyl phosphine, (CH=CH) P; triisopropyl phosphine, (i-C H P; trimethyl phosphine, (CH P;bis Z-diphenylphosphinoethyl) phenyl phosphine,

s 5 2 2 s s 2] 2; 1-diphenylphosphino-2-diphenylarsinoethane,

e s) 2 2 2 B 5) 2; tris Z-diphenylphosphino ethyl) pho sphine, s s) 2 22] 3 cis-bis 1,2-diphenylphosphino) ethylene,

CiS- (C6H5) (C6H5 2; trans-bis( 1,2-diphenylphosphino) ethylene,

trans- (C H PCH1= CHP (C H n-butyldiphenyl phosphine, n-C H P C Hdicyclohexylphenyl phosphine, C H PC H divinylphenyl phosphine, (CH CH)PC H tris(2-ethylhexyl) phosphine, (C H P; tris (p-methoxyphenyl)phosphine, (p-CH O C H P; tri-phenyl phosphine, (C H P; bis-(1,Z-diphenylphosphinoethane) e s 2 2 2 e s 2; trioctyl phosphine, (C HP; methyldiphenyl phosphine, CH P(C H methylene bis-diphenyl phosphine,CH [P (S H tributyl phosphine, (C H P;

pentafluorophenyl-diphenyl phosphine, C H P(C H etc.

and phosphines having active hydrogens such as PH monosubstitutedphosphines or halides, such as RPH RPX and disubstituted phosphines orhalides, R -PH, R PX from which other substituted phosphines or mixedphosphine-t-amine' compounds are prepared, for example, by thewell-known reaction of a phosphine containing a PH group with analdehyde, RCHO, for example formaldehyde, acetaldehyde, propionaldehyde,acrolein, crotonaldehyde in the presence of a secondary amine, R NH, forexample dimethylamine, diethylamine, diallylamine, dipropargylamine,diethanolamine, etc., which in turn are converted to the reactive epoxyonium halide catalysts of this invention by quaternization, as forexample by reaction with a haloepihydrin as illustrated, thus CHzCHCHz]:

(Cn cJZ H CHzO (CH3)2NH o 01 010112011 Hi (CBH5)2PCH2NR3 cflrrmrorrzmonmCHaCHCHa An extraordinary large number of amines are availablecommercially for conversion to the monoand poly-epoxyonium compoundsused in the practice of this invention by the reactions given inEquations 1, 2, 3, and here nabove. A few among the many available fromcommercial sources, listed in the 19701971 Laboratory Guide of theAmerican Chemical Society, Aldrich Chemical Catalogue No. 5, and EastmanOrganic Chemicals List No. 45, are:

trimethylamine, triethylamine, tripropylamine, tributylamine,triallylamine,

tribenzylamine, tridecylamine, triheptylamine, trioctylamine,tripentylamine,

triisopentylamine, N-methyldibenzylamine, N,N-dimethylbenzylamine,

N,N-dimethylallylamine, N,N-diethylallylamine, tripropargylamine,

N,N,N',N'-tetramethyl-2-butene-1,4-diamine,

N,N,N',N-tetramethyl-2-butyne-1,4-diamine,

N,N,N',N'-tetramethyldiaminomethane,

N,N,N',N'-tetramethylethylenediamine,

N,N,N,N'-tetramethyl-l,6-hexanediamine,

N,N,N,N-tetramethyl-1,3-propanediamine,

triethanolamine, triisopropanolamine, N-methyl-N- propargylbenzylamine,

nitrilotriacetonitrile, N(CH CN) N,N,N',N'-tetraethylethylenediamine,

diethylaminoacetonitrile, (C H NCH CN,

2-diethylaminoethanol, Z-dimethylaminoethanol, 2-dimethylaminoethylacetate,

Z-dimethylaminoethyl benzoate, N,N-dimethylglycine diethyl ester,3-dimethylamino-1,2-propanediol, 3-diethylamino-1- propanol,3,3',3"-nitrilopropionamide, pyridine, 2,2'-dipyridyl,

N,N'-dimethylpiperazine, cyclohexyldiethanolamine, N-ethyldibenzylamine,

N-methyldiisobutylamine, N,N,N,N'-2-pentamethyl-1,3-propanediamine,N,N,N,N-tetraallylethylenediamine,N,N,N,N-tetraisopropylethylenediamine, N,N,a-trirnethylbenzylarnine,etc.

The following examples are given by way of illustration and not by wayof limitation of the invention.

EXAMPLE 1 To a reaction vessel equipped with a stirrer, thermometer, gasinlet tube, refrigerated condenser (-20 C.) containing 600 g. ofepichlorohydrin maintained at -5 to 0 C. there is added slowly over theperiod of one hour, g. of trimethylamine, after which the reaction iscontinued at ambient temperature for five hours, yielding a crystallineprecipitate. The crystals are isolated in a dry box, washed with etherand dried in vacuo at 35 C. to yield 240 g. of glycidyltrimethylammonium chloride (Compound A); M.P. 139-141 C.; epoxy number per mole,0.98 (theory, 1.00).

Analysis.Calcd for C H ONCI (percent):

CI 0 l (C H3)aNCHzCH H:

C, 47.5; H, 9.2; C1, 23.4; N, 9.2. Found (percent): C, 47.2; H, 9.4; CI,23.6; N, 9.1.

EXAMPLE 2 In the apparatus of Example 1, a mixture of 30 g. oftriethylamine and 30 g. of epichlorohydrin are stirred at 25 C. forninety-six hours, yielding an oily lower layer which is separated andwashed with ether in a dry box and cooled, yielding 19 g. ofglycidyltriethylammonium chloride (Compound B); M.P. 32-35 C.; epoxynumber per mole 0.98, theory 1.00.

EXAMPLE 3 In a suitable reaction vessel containing 70 ml. of dioxane,there is added 15 g. of trimethylamine and 29 g. of epibromohydrin. Thereaction mixture is maintained at 0-20 C. by external cooling While itis stirred continuously for twenty hours, yielding white crystals whichare collected by filtration in a dry box, washed with ether and dried invacuo at 35 C. to yield 40 g. of glycidyl trimethylammonium bromide(Compound C); M.P. 151- 153 C.; epoxy number per mole, 0.98, theory1.00.

Substitution by 19 g. of trimethylphosphine, B.P. 40 C., for the 15 g.of trimethylamine, in the above procedure, yields the correspondingglycidyl trimethylphosphonium bromide (Compound D),

epoxy number per mole 0.97, theory 1.00, whereas substitution by 25 g.of triethylphosphine, B.P. 127 C., yields glycidyl triethylphosphoniumbromide (Compound E), epoxy number per mole 0.965, theory 1.00.

EXAMPLE 4 By procedures similar to and related to those of Examples l to3, the compounds listed in Column A are converted to onium compounds byreaction with the quaternization agents in Column B.

Column A Column B Column (CH3)2NCH1CH2N(CH3)1 2 ClCHzEIICII; Compound F.

(CHa)zNCH2N(CH3)2 2 BICHZCIICHB Compound G.

(CH )2N(CH2)1N(CHs)2 2 CICHegHgHCHg Compound H.

(CH3)2NCH;CH=CHCHN(CH3)2 2 ICHzQHCHz Compound I.

(CHQ NCH C CCH2N(CH )z 2 BrCHzQHCHz Compound J.

(O6H5)3P ClCHzCHCHz Compound K.

(0411x031 BrOHzCHOHz Compound L.

(CaH)2PCHzCH2P(CaH )2 2 BrCHzCHCH2 Compound M.

EXAMPLE 5 EXAMPLE 7 A series of mixtures of 5.0 g. of3,4-epoxycyclohexyl- A number of polyoxazolidones are prepared usingtolumethyl-3,4-epoxycyclohexane carboxylate (Ciba CY-197) enediisocyanate (T DI) 98%, with various diepoxides and 5.8 g. of toluenediisocyanate is prepared. Mixture A obtained from commercial sources;the ratio of TDI to the is used as a control and to each of theremainder there specific diepoxide being 1:1, in which the equivalentsof is added various amounts of various catalysts, then the thediepoxides are determined by analyses. To perform mixtures are heated at70 C. The polymerization behavior the polymerization 0.01 mole of TDI,1.78 g., 0.01 mole as a function of time is summarized as follows: ofthe diepoxide and 0.2 weight percent on the combined Description ofpolymer at time at 70 0. Weight percent 30 minutes 6 hours 12 hours 24hours 0 No change No change No change No change. 1 Slight increase inviscosity. 3 do do d0 Do.

1 Slightly viscous- Very viscous Soft polymer Hard. 1 Viscous..- Soft;gel Medium hard-.- Do. 1 Soft polymer Hard. Do. 1 -do Do. 1 Do. 1 Do. 1Do. Do. Do. Do. Do. Do. Do.

1 TMAC is tetramethylammonium chloride.

The low molecular weight products obtained in experi- TDI and diepoxideof Catalyst F are placed in glass, ments using TMAC were cloudy,containing undissolved screw-capped vials and flushed with nitrogen andheated TMAC. Similar unsatisfactory results are obtained if inat 85-90C. with agitation until all of the catalyst disstead of TMAC, thecorresponding tetramethylammonium solved in the mixture, then heating iscontinued at 90 C. bromide, (CH NBr, is used. When an amount of ethanolfor two hours during the course of which a considerable equal in weightto the amount of TMAC is used with the increase in viscosity occurs. Thetemperature of reaction TMAC, only a soft polymer is obtained intwenty-four to mixture is then raised at a rate of 10 C. per hour tothirty-six hours. 130 C. and solid, hard, clear castings are obtained.The

EXAMPLE 6 amounts of reagents used with 1.78 g. of TDI are shown in thefollowing table: This example illustrates polymer formation by thereaction of one mole of a bis-epoxy-onium halide with one Eq.wt. GramsCatalyst E,

mole of diisocyanate. There is mixed with 3.0 1 parts of Polyepoxide moLepox' used mg used ethylene bis-(glyc1dyld1rnethylammonium chloride),Com- 1 H) t di 1d 1 1 th pound F, 1.74 parts of toluenediisocyanate andthe mix- 133 266 M8 ture allowed to stand at 25 C.; the mixture becomesirg'l y lghax fiiggde 94 1 7 32 very viscousin twelve hours and hard int hirty six hours. i z g 5 55" When the orlglnal mixture 1s heated at100 C., it becomes (Bakehte FEEL-4205 100 2.00 7. 56 hard in a roximateltwent minutes Blsphmol'Adlglyeidylether P Y Y (Shell Epon 828) no a. 4010.36

When 6.62 parts of ethylene bis-(glycidyldiphenylphos- Resorcinoldiglyeidyl ether phonium bromide), Compound M, is substituted for the(Koppers) 115 3.01 parts of Compound F, the reaction mixture becomes ahard polymer at 100 C. in approximately twelve At the end of the 90 C.heating period, the viscosiminutes. ties of the polymers areparticularly suitable for use as solventless adhesives, potting andencapsulating compounds, impregnants for paper, cloth and glass fabric,chopped fabric, chopped glass fibers and the like; as well as forvarnishes by dilution with such solvents as acetone, dioxane, ethylacetate, etc. At the end of the 110 C. period, the polymers are poorlysoluble in these solvents, but are soluble in aprotic polar solventssuch as dimethylformamide, dimethylacetamide, dimethylsulfoxide and thelike. However, at the end of the 130 C. period, the polymers areinsoluble in the aprotic polar solvents.

Post-curing of the polymer is achieved by heating at 150 C. fortwenty-four hours.

EXAMPLE 8 The procedure of Example 7 is repeated using the phosphoniumCompound M as the catalyst instead of the ammonium Compound F, andsubstantially identical results are obtained, except that the rate ofpolycondensation is slightly lower.

EXAMPLE 9 In 105 parts of dimethylformarnide there is dissolved 17.8parts of Dow epoxy novolac resin DEN438 having the formula CHzHCCHzOOGHQCHCHZ OOHrCHCH: l A l O O O QT WT K Z In 100 parts ofdimethylformamide there is dissolved 13.7 parts of commercialpolymethylene-phenyleneisocywherein n has an average value of 2.1 andthe isocyanate weight is 137, 17.0 parts of Shell Epon 828 and 0.25 partof Compound K and the solution processed by the procedure of Example 9,yielding a viscous varnish.

EXAMPLE 11 The procedure of Example 7 is repeated using instead of TDIan equivalent weight of hexamethylenediisocyanate, 1,5-naphthalenediisocyanate, and 1,4xy1ylidene diisocyanate, respectively, and in allcases, high molecular weight polyoxazolidone polymers are obtained.

EXAMPLE 12 A mixture of 9.4 parts of vinylcyclohexenedioxide, 8.4 partsof toluene diisocyanate and 37 mg. of catalyst A or 45 mg. of catalyst Eare heated with stirring at 90 C. under nitrogen until a very viscousbut flowa-ble polycondensation is obtained. Then a thin layer of thisviscous intermediate is spread as an adhesive between (1) overlappingglass slides, (2) two strips of aluminum, (3) two strips of copper,

16 and the sandwiches heated at C. for ten hours. In all cases tenaceousbonds are obtained.

EXAMPLE 13 The reactants used in Example 12 are mixed and heated undernitrogen at 90 C. until a homogeneous mixture is obtained which is thencooled to room temperature. The slightly viscous mass is then pouredover electrical components fixed in a metal container which is degassedunder a reduced pressure of 5 mm. Hg pressure at 30 C. and placed in aheating chamber in which the temperature is raised at a rate of 10 C.per hour to C., at which temperature it is cured for five hours. Avoid-free, waterand moisture-proof encapsulation is obtained.

What is claimed is:

1. A process for preparing a polyoxazolidone which comprises reacting apoly(l,2-epoxide) with an organic polyisocyanate in the presence of atleast 0.005 percent by weight, based upon the combined weight of saidepoxide and said isocyanate reactants, of an organic onium halideselected from the class of ammonium and phosphonium halides possessingat least one and no more than four oxirane groups, said onium halidebeing selected from the class of compounds having the formulas wherein Qrepresents an atom selected from the class consisting of P and N,

n represents an integer having a value of zero to ten,

n represents an integer having a value of one or two,

n" represents an integer having a value of one to three,

X represents a halogen, and

when n is one, Y represents R, and

when n' is two, Y represents R.

wherein R represents a monovalent aliphatic hydrocarbon radicalcontaining at least one and no more than ten carbon atoms,

R is a radical selected from the class consisting of R radicals andaromatic hydrocarbon radicals containing at least six and no more thantwelve carbon atoms, and

R" represents a divalent aliphatic or aromatic hydrocarbon radicalcontaining at least one and no more than twelve carbon atoms.

2. The process of claim 1 in which the onium halide is 3. The process ofclaim 2 in which the polyisocyanate is an aryl diisocyanate.

4. The process of claim 2 in which the polyisocyanate is toluenediisocyanate.

5. The process of claim 2 in which the polyepoxide isGHQ/1001130CsH4C(CHa)zC H4OCHzCHCH '6. The product produced according toprocess of claim 2.

7. The product of claim 6 in which the reaction mixture consistsessentially of a diisocyanate and a depoxide and an onium halide inwhich n is one.

8. The product of claim 6 in which the reaction mixture consistessentially of a diisocyanate and a diepoxide and an onium halide inwhich n' is two.

9. The product of claim 8 in which the onium halide represents at least0.05 molar percent of the diepoxide concentration.

10. The condensation product of claim 7 in which said reactants comprisean organic polyisocyanate and a compound of the formula 11. The processof claim 2 in which both said polyisocyanate and said poly(1,2-epoxide)are bifunctional.

12. The process of claim 11 in which the onium halide contains oneoxiraue group.

13. The process of claim 11 in which the onium halide contains twooxirane groups.

14. The process of claim 1 in which Q is nitrogen.

15. The process of claim 1 in which Q is phosphorus.

16. The process of claim 1 in which n is one.

17. The process of claim 1 in which n is two.

References Cited UNITED STATES PATENTS 2,131,120 9/1938 Schlack 260-23,510,246 5/1970 Keen et al 260-5676 3,020,262 2/1962 Speranza 260-47WILLLAM H. SHORT, Primary Examiner T. E. PERTILLA, Assistant ExaminerUS. Cl. X.R.

117-124 E, 128.4, 127, 155 R, 1 69 R; 260-9, .18 PF, 37 EP, 59.67 TN,77.5 AB, 831, 834

